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Reconstructing solute-induced phase transformations within individual nanocrystals

Nature Materials volume 15, pages 768–774 (2016)Cite this article

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Abstract

Strain and defects can significantly impact the performance of functional nanomaterials. This effect is well exemplified by energy storage systems, in which structural changes such as volume expansion and defect generation govern the phase transformations associated with charging and discharging. The rational design of next-generation storage materials therefore depends crucially on understanding the correlation between the structure of individual nanoparticles and their solute uptake and release. Here, we experimentally reconstruct the spatial distribution of hydride phases within individual palladium nanocrystals during hydrogen absorption, using a combination of electron spectroscopy, dark-field imaging, and electron diffraction in an environmental transmission electron microscope. We show that single-crystalline cubes and pyramids exhibit a uniform hydrogen distribution at equilibrium, whereas multiply twinned icosahedra exclude hydrogen from regions of high compressive strains. Our technique offers unprecedented insight into nanoscale phase transformations in reactive environments and can be extended to a variety of functional nanomaterials.

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Figure 1: Structural characterization and EELS of individual palladium nanoparticles.
Figure 2: EELS loading isotherms.
Figure 3: STEM-EELS maps of hydrogen distribution within nanoparticles.
Figure 4: Sub-particle pressure–lattice expansion isotherms.

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Acknowledgements

We gratefully acknowledge scientific feedback and discussions with all Dionne group members and R. Griessen. J.A.D. acknowledges support from a PECASE Award administered by the Air Force Office of Scientific Research (FA9550-15-1-0006) and a National Science Foundation CAREER Award (DMR-1151231). Funding from a Camille and Henry Dreyfus grant is gratefully acknowledged, as is salary support from an NSF CAREER Award (DMR-1151231) and a PECASE grant (FA9550-15-1-0006). This work was supported in part by a SLAC National Accelerator Laboratory LDRD award in concert with the Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering, under contract DE-AC02-76SF00515. Work was also supported by the research programme ‘Fellowships for Young Energy Scientists’ (YES!) of the Foundation for Fundamental Research on Matter (FOM), which is financially supported by the Netherlands Organisation for Scientific Research (NWO), and by an award from the Department of Energy (DOE) Office of Science Graduate Fellowship Program administered by the Oak Ridge Institute for Science and Education for the DOE. ORISE is managed by Oak Ridge Associated Universities (ORAU) under DOE contract number DE-AC05-06OR23100. All opinions expressed in this paper are the authors’ and do not necessarily reflect the policies and views of DOE, ORAU, or ORISE. Part of this work was performed at the Stanford Nano Shared Facilities (SNSF).

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Author notes

  1. Tarun C. Narayan and Andrea Baldi: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Materials Science and Engineering, Stanford University, 496 Lomita Mall, Stanford, California 94305, USA

    Tarun C. Narayan, Andrea Baldi, Robert Sinclair & Jennifer A. Dionne

  2. Dutch Institute for Fundamental Energy Research (DIFFER), De Zaale 20, 5612 AJ Eindhoven, The Netherlands

    Andrea Baldi

  3. Stanford Nano Shared Facilities, Stanford University, Stanford, California 94305, USA

    Ai Leen Koh

  4. Stanford Institute for Materials and Energy Sciences, SLAC National Accelerator Laboratory, Menlo Park, California 94025, USA

    Jennifer A. Dionne

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  1. Tarun C. Narayan
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Contributions

All authors contributed to the design of the experiment. T.C.N., A.B. and A.L.K. carried out the experiment. T.C.N. and A.B. wrote the first draft of the manuscript and all authors assisted in the writing process and data analysis.

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Correspondence to Jennifer A. Dionne.

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Narayan, T., Baldi, A., Koh, A. et al. Reconstructing solute-induced phase transformations within individual nanocrystals. Nature Mater 15, 768–774 (2016). https://doi.org/10.1038/nmat4620

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